Insecticidal compositions comprising a polychloro chloromethyl 2, 5 endomethylene cyclohexene 3



'CZZZA ?atented Feb. 25, 1952 INSECTICIDAL COMPOSITIONS COMPRIS- ING APOLYCHLORO CKLOROMETHYL 3- ENDOMETHYLENE CYCLOHEXENE 3 Allen B.Klttlcson, Cranford, andAnthony'H; Gleason, Westllcld, N. 3., aaslgnonto Standard Oil Development Company, a corporation of Delaware NoDrawing. Application on, 22, 1048,

. Serial No. 28.758

5- Claims. (Cl. 167-30) This invention relates to new and usefulimprovements in insecticidal preparations. This invention also relatesto methods of protecting organic material subject to attack by loworders of organisms.

It has now been found that polychlorinated compounds made fromchloromethyl 2,5 endo methylene cyclohexene-3 and especially thesecompounds having from 50 to 75% chlorine;

be used. comprise the sulfates of long-chain based on the weight of thechlorinated product are ex remely effective for killing and repellinginsects.

These compounds are especially efiective against destructive chewinginsects such as the Mexican bean beetle, the Colorado potato beetle andcaterpillars. Sincethe compositions of these inventions arenon-phytotoxic, they may be applied directly to a wide variety of plantsto protect them from injurious insects.

The preparation of chloromethyl 2,5 endomethylene cyclohexene-3 is knownand is given in the literature (K. Alder and E. Windemuth; Ber. 7118,.(1939) (1938)). One of the methods of preparing it is by thecondensation of allyl chloride with mono or dicyclopentadiene;

The chlorinated products arethen prepared by the chlorination of thechloromethyl 2,5 endomethylene cyclohexene-S-z The polychlorinatedcompounds of chloromethyl 2,5. endomethylene cyclohexene-E are strawcolored viscous oils-soluble. in acetone, petroleum ether,

. benzene, carbon tetrachloride and other organic solvents.

Chloromethyl 2,5 endomethylene cyclohexene- 3-may be chlorinated in thepresence or absence of a solvent. Suitable solvents for the chlorinationare-chloroform; carbon tetrachloride. etc. Theinitial stages of thechlorination may. be carried out at room temperature or lower. To

attain a more rapid rate of reaction at the higher the chlorine'contentbecomes less than 50% or' more than I5%.

The compounds of this invention may be adsorbed on a solid carrier suchas clay, talc and I bentoniteto be applied as a diluted dust. They mayalso be applied as aspray in a liquid carrier either as a solution in-asolvent or as a suspension in a non-solvent such as water: when appliedas aspray in-water. it may be desirable to incorporates. wetting agent.

The water-soluble wetting agents that ma alcohols such as 'dcdecanol upto octadecanol, sulfonated amide and; esterderivatives,- suitonatedaromatic and :nixedalkyl-aryi sulfonate derivatives, esters of fattyacids such as ricinoleic 5 acid ester of sorbitol, andpetroieum-sulfonates of Cm to C length. The non-ionic emulsifying agentssuch as the ethylene oxide condensation products of .aikylated phenolsmay also be used. It is to be'understood that these and similar 0compounds are intended when theterm wettin agentisused hereafter. 1

-The compounds of this invention may also be admixed withcarriersthat-are themselvesactive such as parasificides, hormones,-herbi- -15 cides, fertilizers andwetting agents,-v stomach and'contact-insecticides such as the: arsenatest fluorides, rotenone-andthe-variousflsh -poisons and organic insecticides-such. asdichlorodiphenyltrichloroethane. .Benzeneehexachloride and-"similarproducismay also be advan tageously added;

This invention wili't be' better-understobd by' reference to thefollowing-examples oi thepreparation'ot the compounds of. thisinvention; and their use for the statedspurposet chloromethyl 2,5"endomethylenecyclohenene- 3 ('11- g.) was-charged to a 500 cc.- s-n'ecked. 40. quartz flask equipped-- with a stirrer, .thrmometer,reflux condenser andinlettube-for chlorine.

Chlorine was. bubbled into the rapidly-stirredliquidstarting'at'roomgtemperature. The temperature rapidly inc-retreats '80- 0. due toheat of Y 46. reaction- During them-st two hours oil-reaction thetemperature was maintained-at -80 C. by occasional cooling. The rate or,chlorino absorption then decreased and the temperature dropped to 50 C.The chlorination was-con 50 tinned at ISO- 0., using ultraviolet lightto catalyze the reaction. Samples A;.B and C: were mime-an The houseflytoxicity (Nelson Drop Test) gives the per cent mortality after 24 hoursfollowing application of 0.002 cc. of the specified concentration oi thetest material (in acetone) on the fly's body.

. aryl derivatives. and petroleum sultonates of C10 to C length.

, 3. An insecticidal composition comprising as an active ingredient apolychloro chloromethyl 2,5 endomethylene cyclohexene-ii containing from50 to 75% by weight of chlorine admixed with an inert, finely divided,solid diluent, said active ingredient being prepared by a process whichcomprises treating chloromethyl 2,5 endomethylene cyclohexene-3 withchlorine at a temperature between about 20 and 100 C. in the presence ofultraviolet light.

4. An insecticidal composition comprising as an active ingredient apolychloro chloromethyi 2,5 endoinethylene cyclohexene-3 containing from50 to 75% by weight oi chlorine admixed with a powdered clay, saidactive ingredient being prepared by a process which comprises treatingchlorornethyl 2,5 endomethylene cyclohexene-3 with chlorine at atemperature between about Table Bloodstream Insecti- ContactInsecticidal Housefly Toxicity Activity (Per cent Kill) 253" (Per NelsonDrop Test Samples of Chlorinated (;hl0r0i1;lleliby1%5 Eln- P Hp t omei.y ene .-yo 0- Blauua, omdpmua 2 am us emu cana hcxened germanim sou-Btu!(American Roach) cgrgtoi Per Cent (German (Milkweed (pd Kill Roach) Bug)Male Female A 100 mo 100 100' l 5 100 B m0 100 m0 100 fig g 5 c 100 100100 100 M 75 Control (Pyrethrins). .04 40 It should be noted that thecompounds of this invention were much more effective than pyrethrins infly toxicity.

It is to be understood that the invention is not limited to the specificexamples which have been oifered merely as illustration and thatmodification may be made within the scope of the appended claims withoutdeparting irom the spirit of the invention.

What is claimed is: v

1. An. insecticidal composition comprising as an active ingredient apolychloro chloron'iethyl 2,5 endomethylene cyclohexene-3 containingfrom to 75% by weight of chlorine admixed with an emulsifying agentwhich lowers the surface tension of water and thereby promotes aqueousemulsions of the active ingredient. said active ingredient beingprepared by a process which comprises treating chloromethyl 2,5endomethylene cyclohexene-3 with chlorine at a temperature between about20 and 100 C. in the presence of ultraviolet light. I

2. A composition as in claim 1 in which the emulsifying agent isselected from the group consisting of long chain alcohol sulfates,sultonated amide derivatives, sulionated ester derivatives,- sulfonatedaromatic derivatives, sulionated alicyl- 20 and C. in the presence ofultraviolet light. 5. An insecticidal composition as in claim 4 in 40which the clay is bentonite.

ALLEN R. KITTLESON- ANTHONY H. GLEASON.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS I Date University of Delaware Agr. Expt. Stat,February 1947.

Desalbres et al.: Chimie et Industrie, vol. 58, pp. 443-448 (1947).

1. AN INSECTICIDAL COMPOSITION COMPRISING AS AN ACTIVE INGREDIENT APOLYCHLORO CHLOROMETHYL 2,5 ENDOMETHYLENE CYCLOHEXENE-3 CONTAINING FROM50 TO 75% BY WEIGHT OF CHLORINE ADMIXED WITH AN EMULSIFYING AGENT WHICHLOWERS THE SURFACE TENSION OF WATER AND THEREBY PROMOTES AQUEOUSEMULSTIONS OF THE ACTIVE INGREDIENT, SAID ACTIVE INGREDIENT BEINGPREPARED BY A PROCESS WHICH COMPRISES TREATING CHLOROMETHYL 2,5ENDOMETHYLENE CYCLOHEXENE-3 WITH CHLORINE AT A TEMPERATURE BETWEEN ABOUT20 AND 100* C. IN THE PRESENCE OF ULTRAVIOLET LIGHT.